EP1326904B1 - Procede de preparation de latex caoutchouteux greffes ayant une teneur limitee en monomeres residuels - Google Patents

Procede de preparation de latex caoutchouteux greffes ayant une teneur limitee en monomeres residuels Download PDF

Info

Publication number
EP1326904B1
EP1326904B1 EP01986308A EP01986308A EP1326904B1 EP 1326904 B1 EP1326904 B1 EP 1326904B1 EP 01986308 A EP01986308 A EP 01986308A EP 01986308 A EP01986308 A EP 01986308A EP 1326904 B1 EP1326904 B1 EP 1326904B1
Authority
EP
European Patent Office
Prior art keywords
initiator
time interval
graft rubber
added
total
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01986308A
Other languages
German (de)
English (en)
Other versions
EP1326904A1 (fr
Inventor
Hans-Erich Gasche
Herbert Eichenauer
Pierre Vanhoorne
Ulrich Jansen
Eckhard Wenz
Stefan Moss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Styrolution Jersey Ltd
Original Assignee
Ineos ABS Jersey Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ineos ABS Jersey Ltd filed Critical Ineos ABS Jersey Ltd
Publication of EP1326904A1 publication Critical patent/EP1326904A1/fr
Application granted granted Critical
Publication of EP1326904B1 publication Critical patent/EP1326904B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the invention relates to a process for the preparation of graft rubber polymers of the ABS type by emulsion polymerization by the so-called feed-batch process, wherein latexes are obtained with significantly reduced residual monomer contents and compositions containing said graft rubber polymers.
  • the polymers thus prepared have no negative effects on the other properties.
  • the matrix resin I can be readily prepared by radical polymerization in solution or suspension or by bulk polymerization, it is necessary to produce the graft rubber polymer II by emulsion polymerization using rubber latices having the required average particle diameters to produce glossy molded articles to form finely divided polymers having average particle diameters d 50 to obtain from about 0.08 to 0.5 microns.
  • WO-A 19741 188 the use of long-chain, surface-active initiator components to reduce the residual monomers.
  • WO-A 00/12569 recommends the use of combinations of an oxidizing agent, a reducing agent prepared from aldehyde and inorganic dithionite and polyvalent metal ions for the treatment of polymer dispersions, while WO-A 00/14123 the treatment with an initiator system of an oxidizing agent and an ⁇ -hydroxycarbonyl compound will be described.
  • all of these measures require the use of new adjuvant components, which usually undesirably alter the properties of the graft rubber polymers.
  • US 4200593 describes a process for producing ABS-type graft rubber polymers by dispersion polymerization.
  • EP 0281174 describes a process based on 2 stages for the polymerization of vinylaromatic and acrylonitrile in the presence of polybutadiene rubber.
  • EP 0046320 describes a process for the polymerization of vinyl aromatic, acrylonitrile and polybutadiene.
  • graft rubber polymers of the ABS type can be prepared by emulsion polymerization by the feed batch process with significantly reduced residual monomer contents using conventional free-radical initiator systems without the addition of novel substances, if during the reaction a special way of adding the initiator components is maintained ,
  • the minimum of added initiator or initiator system is run through per time interval in the first half of the total reaction time.
  • the minimum is passed through in the first or second third of the total reaction time.
  • the practical implementation of the process according to the invention is usually carried out by initially charging a rubber latex or a mixture of rubber latices in a stirred reactor, heating the reactor contents to a temperature suitable for initiating polymerization with free-radical initiators, adding the free-radical initiator in the manner indicated above, metering in the grafting monomers and optionally parallel metered addition of an aqueous emulsifier solution.
  • Suitable rubbers when using the process according to the invention for the preparation of graft rubber polymers are in principle all rubbery polymers present in emulsion form having a glass transition temperature below 0 ° C.
  • polybutadiene rubbers SBR rubbers having up to 30% by weight of copolymerized styrene and acrylate rubbers, especially those which have a core-shell structure, for example as in DE-A 3 006 804 described.
  • latices having average particle diameters d 50 from 0.05 to 2.0 .mu.m, preferably from 0.08 to 1.0 .mu.m and particularly preferably from 0.1 to 0.5 .mu.m are suitable .
  • the gel contents of the rubbers used in wide Limits are varied, preferably they are between 30 and 95 wt .-% (determined by wire cage method in toluene.
  • the rubber latex (a) preferably has a width of the particle size distribution of 30 to 100 nm, more preferably 40 to 80 nm, the rubber latex (b) of 50 to 500 nm, particularly preferably 100 to 400 nm (measured in each case as d 90 -d 10 value from the integral particle size distribution).
  • the mixtures preferably contain the rubber latices (a) and (b) in a weight ratio of 90:10 to 10:90, particularly preferably 60:40 to 30:70 (in each case based on the respective solids content of the latices).
  • the mean particle diameters are determined by means of ultracentrifuge (cf. W. Scholtan, H. Lange: Colloid-Z. u Z. Polymers 250, p. 782-796 (1972 ) certainly.
  • the rubber latices used can be prepared by emulsion polymerization, the required reaction conditions, auxiliaries and working techniques are basically known.
  • emulsifiers the usual anionic emulsifiers such as alkyl sulfates, alkyl sulfonates, aralkylsulfonates, soaps of saturated or unsaturated fatty acids (eg oleic acid, stearic acid) and alkaline disproportionated or hydrogenated abietic or tall oil can be used, preferably emulsifiers with carboxyl group (eg salts of C 10 -C 18- fatty acids, disproportionated abietic acid, emulsifiers according to DE-A 36 39 904 and DE-A 39 13 509 ) used.
  • carboxyl group eg salts of C 10 -C 18- fatty acids, disproportionated abietic acid, emulsifiers according to DE-A 36 39 904 and DE-A 39 13 509
  • rubber polymer latices can also be prepared by emulsifying finished rubber polymers in aqueous media (see Japanese Patent Application JP-A 55 125 102 ).
  • Examples of preferred compounds of the formula (I) are styrene, ⁇ -methylstyrene, p-methylstyrene and vinyltoluene.
  • Preferred compounds of the formula (II) are acrylonitrile and methyl methacrylate.
  • Further monomers which are suitable in principle are, for example, vinyl acetate and N-phenylmaleimide.
  • Preferred monomers are mixtures of styrene and acrylonitrile, ⁇ -methylstyrene and acrylonitrile, of styrene, acrylonitrile and methyl methacrylate and combinations of these monomer mixtures with N-phenylmaleimide.
  • Preferred graft polymers prepared according to the invention are those obtained by graft polymerization of styrene and acrylonitrile in a ratio by weight of 90:10 to 50:50, preferably 80:20 to 65:35 (where styrene can be wholly or partly replaced by ⁇ -methylstyrene or methyl methacrylate ) in the presence of such amounts of rubber, preferably polybutadiene, that graft polymers having rubber contents of 30 to 80 wt .-%, preferably 35 to 75 wt .-% and particularly preferably 35 to 70 wt .-% result.
  • Suitable initiators are inorganic and organic peroxides, ZBH 2 O 2, di-tert-butyl peroxide, cumene hydroperoxide, dicyclohexyl percarbonate, p-menthane hydroperoxide, tert-butyl hydroperoxide, azo initiators such as azobisisobutyronitrile, inorganic persalts such as potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium, sodium and redox systems, which are composed of a - usually organic - oxidizing agent and a reducing agent, wherein in the reaction medium additionally heavy metal ions may be present (see H. Logemann in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1, pp. 263-297 ).
  • Preferred initiators are potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate or mixtures thereof and also cumene hydroperoxide, p-menthane hydroperoxide, tert-butyl hydroperoxide or mixtures thereof.
  • Reducing agents which can be used according to the invention are preferably water-soluble compounds having a reducing action, preferably selected from the group of the salts of sulfinic acid, salts of sulfurous acid, sodium dithionite, sodium sulfite, sodium hyposulfite, sodium hydrogensulfite, ascorbic acid and salts thereof, Rongalit C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacetone, sugars (eg glucose or dextrose).
  • a reducing action preferably selected from the group of the salts of sulfinic acid, salts of sulfurous acid, sodium dithionite, sodium sulfite, sodium hyposulfite, sodium hydrogensulfite, ascorbic acid and salts thereof, Rongalit C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacetone, sugars (eg glucose or dextrose).
  • iron (II) salts such as iron (II) sulfate, tin (II) salts such as tin (II) chloride, titanium (III) salts such as titanium (III) - sulfate; however, preferably no such metal salts are used.
  • Particularly preferred reducing agents are dextrose, ascorbic acid (salts) or sodium formaldehyde sulfoxylate (Rongalit C).
  • the reaction temperature in the application of the process according to the invention for the preparation of graft rubber polymers can be varied within wide limits. It is generally 25 ° C to 160 ° C, preferably 40 ° C to 90 ° C and particularly preferably 50 ° C to 85 ° C.
  • the graft polymerization is carried out so that the temperature difference between the beginning and end of the reaction is at least 10 ° C, preferably at least 15 ° C and more preferably at least 20 ° C.
  • 0.05 to 1.00 parts by weight (per 100 parts by weight of grafting monomer), preferably 0.08 to 0.8 parts by weight (per 100 parts by weight of grafting monomer) of one or more of the graft monomers may be used together with the grafting monomers Mercaptans are added.
  • Suitable mercaptans are for.
  • aliphatic mercaptans such as ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, tert Dodecyl, n-hexadecyl and n-octadecyl mercaptan or aromatic mercaptans such as thiophenol.
  • Preferred mercaptans are tert-dodecylmercaptan and n-dodecylmercaptan and mixtures thereof.
  • molecular weight regulating substances such as dimeric ⁇ -methylstyrene or terpinolene in amounts of 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight (in each case per 100 parts by weight of grafting monomer) are used.
  • the above-mentioned compounds can be used as the emulsifier in the graft polymerization reaction.
  • the process according to the invention achieves the desired effect of a reduced residual monomer amount at the end of the graft polymerization reaction using conventional free-radical initiator systems, if the initiator system is added in portions or continuously to the reaction mixture in such a way that a minimum of initiator metered in is passed through during the reaction.
  • the graft rubber polymers prepared by the process according to the invention preferably have a rubber content of 30 to 80 wt .-%, particularly preferably from 35 to 75%.
  • the graft rubber polymer prepared according to the invention and customary working up is mixed with at least one rubber-free matrix resin.
  • the rubber-free copolymers used are preferably copolymers of styrene and acrylonitrile in a weight ratio of 95: 5 to 50:50, where styrene and / or acrylonitrile can be wholly or partly replaced by ⁇ -methylstyrene, methyl methacrylate or N-phenylmaleimide.
  • copolymers preferably have average molecular weights M w from 20,000 to 200,000 or intrinsic viscosities [ ⁇ ] of 20 to 110 ml / g (measured in dimethylformamide at 25 ° C).
  • thermoplastic resins made from vinyl monomers the use of polycondensates, e.g. aromatic polycarbonates, aromatic polyester, polyesters, polyamides as a rubber-free copolymer in the molding compositions according to the invention possible.
  • polycondensates e.g. aromatic polycarbonates, aromatic polyester, polyesters, polyamides as a rubber-free copolymer in the molding compositions according to the invention possible.
  • the molecular weight can be adjusted in a known manner by an appropriate amount of known chain terminators.
  • Suitable diphenols of formulas (III) and (IV) are e.g. Hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) hydroxy-3,5-dimethylphenyl) -propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) -propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) -propane , 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5,5-tetramethylcyclohe
  • Preferred diphenols of the formula (III) are 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, and the preferred phenol of the formula (IV) is 1,1-bis (4-hydroxyphenyl) -cyclohexane. (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Suitable chain terminators are, for example, phenol, p-tert-butylphenol, long-chain alkylphenols such as 4- (1,3-tetramethyl-butyl) phenol according to DE-OS 2,842,005 , Monoalkylphenols, dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-OS 3 506 472 such as p-nonylphenol, 2,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) -phenol and 4- (3,5-dimethylheptyl) - phenol.
  • the required amount of chain terminators is generally 0.5 to 10 mol%, based on the sum of diphenols (III) and (IV).
  • the suitable polycarbonates or polyester carbonates may be linear or branched; branched products are preferably obtained by incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those having three or more than three phenolic OH groups ,
  • the suitable polycarbonates or polyester carbonates may contain aromatically bonded halogen, preferably bromine and / or chlorine; preferably they are halogen-free.
  • M w average molecular weights
  • Suitable thermoplastic polyesters are preferably polyalkylene terephthalates, i.e., reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g., dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.
  • polyalkylene terephthalates i.e., reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g., dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.
  • Preferred polyalkylene terephthalates can be prepared from terephthalic acids (or their reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods ( Plastics Handbook, Volume VIII, p. 695 ff, Carl Hanser Verlag, Kunststoff 1973 ).
  • polyalkylene terephthalates are 80 to 100, preferably 90 to 100 mol% of the dicarboxylic acid residues, terephthalic acid residues and 80 to 100, preferably 90 to 100 mol% of the diol residues, ethylene glycol and / or butanediol-1,4 residues.
  • the preferred polyalkylene terephthalates may contain 0 to 20 mol% of radicals of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 12 C atoms, for example radicals of propanediol-1, 3, 2-ethylpropane-1,3-diol, neopentyl glycol, pentanediol-1,5, 1,6-hexanediol, cyclohexanedi-methanol-1,4, 3-methyl-pentanediol-1,3 and -1,6, 2-ethylhexanediol-1 , 3,2,2-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di ( ⁇ -hydroxyethoxy) -benzene, 2,2-bis-4-hydroxycyclohexyl
  • the polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or of tri- or tetrabasic carboxylic acids, as described in US Pat DE-OS 1 900 270 and the U.S. Patent 3,692,744 are described to be branched.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. It is advisable to use not more than 1 mol% of the branching agent, based on the acid component.
  • polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters prepared from at least two of the abovementioned alcohol components: particularly preferred copolyesters are poly (ethylene glycol butane-1,4-diol) terephthalates.
  • the preferably suitable polyalkylene terephthalates generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, in particular 0.6 to 1.2 dl / g, each measured in Phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
  • Suitable polyamides are known homopolyamides, copolyamides and mixtures of these polyamides. These may be partially crystalline and / or amorphous polyamides.
  • Polycrystalline polyamides which are suitable are polyamide-6, polyamide-6,6, mixtures and corresponding copolymers of these components. Also suitable are partially crystalline polyamides whose acid component is wholly or partially composed of terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, the diamine component thereof wholly or partly from m- and / or p-xylylenediamine.
  • polyamides which are wholly or partly made of lactams having 7-12 carbon atoms in the ring, optionally with the concomitant use of one or more of the abovementioned starting components.
  • Particularly preferred semi-crystalline polyamides are polyamide-6 and polyamide-6,6 and their mixtures.
  • amorphous polyamides known products can be used. They are obtained by polycondensation of diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, m- and / or p-xylylenediamine, bis (4-aminocyclohexyl) - methane, bis (4-aminocyclohexyl) propane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 3-aminomethyl, 3,5,5-trimethylcyclohexylamine, 2,5- and / or 2, 6-bis (aminomethyl) norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as oxalic acid,
  • Copolymers obtained by polycondensation of a plurality of monomers are also suitable, and copolymers which are prepared with the addition of aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoundecanoic acid or ⁇ -aminolauric acid or their lactams.
  • aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoundecanoic acid or ⁇ -aminolauric acid or their lactams.
  • Particularly suitable amorphous polyamides are the polyamides prepared from isophthalic acid, hexamethylenediamine and further diamines such as 4,4'-diaminodicyclohexylmethane, isophoronediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, 2,5- and / or 2 norbornene, 6-bis (aminomethyl); or from isophthalic acid, 4,4'-diamino-dicyclohexylmethane and ⁇ -caprolactam; or isophthalic acid, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and the mixture of isomers of 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine.
  • isophthalic acid, hexamethylenediamine and further diamines such as 4,4'-di
  • the pure 4,4'-diaminodicyclohexylmethane it is also possible to use mixtures of the positionally isomeric diaminodicyclohexylmethanes which are composed 70 to 99 Mole% of the 4,4'-diamino isomer 1 to 30 Mole% of the 2,4'-diamino isomer 0 to 2 Mole% of the 2,2'-diamino isomer and optionally correspondingly higher condensed diamines, which are obtained by hydrogenation of diaminodiphenylinethane technical grade.
  • the isophthalic acid may be replaced by terephthalic acid up to 30%.
  • the polyamides preferably have a relative viscosity (measured on a 1 wt .-% solution in m-cresol at 25 ° C) of 2.0 to 5.0, more preferably from 2.5 to 4.0.
  • the graft rubbers produced according to the invention are used in amounts of from 1 to 80% by weight, based on the total molding composition.
  • the graft rubber polymer produced according to the invention can be mixed with the matrix resin in various ways. If the matrix resin is prepared by emulsion polymerization, the latices can be mixed and precipitated together or else precipitated separately and the resulting solids are mixed.
  • the graft rubber polymer must be precipitated separately.
  • known methods are used, for example addition of salts and / or acids, after which the precipitated products are washed, dried and, if appropriate, converted from the powder form into a granular form.
  • Mixing devices for precipitates or granulates are e.g. Multi-roll chairs, mixing extruders or internal kneaders into consideration.
  • the necessary or suitable additives may be added to the molding compositions according to the invention, e.g. Antioxidants, UV stabilizers, Peroxidzerstörer, antistatic agents, lubricants, mold release agents, flame retardants, fillers or reinforcing materials (glass fibers, carbon fibers, etc.), colorants.
  • Antioxidants e.g. UV stabilizers, Peroxidzerstörer, antistatic agents, lubricants, mold release agents, flame retardants, fillers or reinforcing materials (glass fibers, carbon fibers, etc.), colorants.
  • the final deformation can be carried out on commercially available processing units and includes, for example, injection molding, sheet extrusion with optional subsequent hot deformation, cold working, extrusion of pipes and profiles, calendering.
  • the latex is cooled to 23 ° C; Subsequently, the residual monomers are determined by gas chromatography according to the head-space technique. The values are also given in Table 1.
  • the graft rubber production process according to the invention has no negative effects on the properties of the graft rubber polymers or products containing them.
  • the latex is cooled to 23 ° C; Subsequently, the residual monomers are determined by gas chromatography according to the head-space technique. The values are also given in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerization Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Claims (11)

  1. Procédé pour la préparation de polymères caoutchouc greffés du type ABS par polymérisation en émulsion d'après le procédé d'alimentation dans la charge, caractérisé en ce que l'initiateur, respectivement le système d'initiateur, utilisé pour le déclenchement de la polymérisation est ajouté au mélange réactionnel par portions ou en continu de telle sorte qu'au cours de la réaction, un minimum d'initiateur, respectivement de système d'initiateur, ajouté par intervalle de temps est traversé et en ce que dans au moins 50 % du temps total de réaction, la quantité d'initiateur ajoutée dans chaque intervalle de temps correspond au moins à une part de ≥ 0,5 % en poids de la quantité totale d'initiateur, le temps total de réaction comprenant n intervalles de temps, avec n = 3 à 20 et chaque intervalle de temps ayant une durée de 5 à 90 minutes.
  2. Procédé pour la préparation de polymères caoutchouc greffés du type ABS par polymérisation en émulsion d'après le procédé d'alimentation dans la charge, caractérisé en ce que l'initiateur, respectivement le système d'initiateur, utilisé pour le déclenchement de la polymérisation est ajouté au mélange réactionnel par portions et en continu de telle sorte qu'au cours de la réaction un minimum d'initiateur, respectivement de système d'initiateur, ajouté par intervalle de temps est traversé et en ce que dans au moins 70 % du temps total de réaction, la quantité d'initiateur ajoutée dans chaque intervalle de temps correspond au moins à une part de ≥ 1 % en poids de la quantité totale d'initiateur, le temps total de réaction comprenant n intervalles de temps, avec n = 3 à 15 et chaque intervalle de temps ayant une durée de 10 à 80 minutes.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que le minimum d'initiateur, respectivement de système d'initiateur, ajouté par intervalle de temps est traversé pendant la première moitié du temps total de réaction.
  4. Procédé selon les revendications 1 et 2, caractérisé en ce que le minimum d'initiateur, respectivement de système d'initiateur ajouté par intervalle de temps est traversé pendant le premier ou le deuxième tiers du temps total de réaction.
  5. Procédé selon les revendications 1 à 4, caractérisé en ce que du peroxydisulfate de potassium, du peroxydisulfate de sodium, du peroxydisulfate d'ammonium ou des mélanges de ceux-ci sont utilisés comme initiateur.
  6. Procédé selon les revendications 1 à 4, caractérisé en ce qu'une combinaison de peroxyde organique et de dextrose et/ou d'acide ascorbique est utilisée comme système d'initiateur.
  7. Procédé selon la revendication 6, caractérisé en ce que de l'hydroperoxyde de cumène, de l'hydroperoxyde de p-menthane, de l'hydroperoxyde de tert.-butyle ou des mélanges de ceux-ci sont utilisés comme peroxydes.
  8. Polymère caoutchouc greffé pouvant être obtenu par polymérisation en émulsion d'après le procédé d'alimentation dans la charge, caractérisé en ce que l'initiateur, respectivement le système d'initiateur, utilisé pour le déclenchement de la polymérisation est ajouté au mélange réactionnel par portions ou en continu de telle sorte qu'au cours de la réaction un minimum d'initiateur, respectivement de système d'initiateur, ajouté par intervalle de temps est traversé et en ce que dans au moins 50 % du temps total de réaction, la quantité d'initiateur ajoutée dans chaque intervalle de temps correspond au moins à une part de ≥ 0,5 % en poids de la quantité totale d'initiateur, le temps total de réaction comprenant n intervalles de temps, avec n = 3 à 20 et chaque intervalle de temps ayant une durée de 5 à 90 minutes.
  9. Utilisation des polymères caoutchouc greffés de type ABS pouvant être obtenus selon les revendications 1 à 8 à la préparation de matières de moulage thermoplastiques modifiées par caoutchouc.
  10. Matières de moulage thermoplastique contenant des polymères caoutchouc greffés du type ABS selon les revendications 1 à 8.
  11. Pièces moulées pouvant être obtenues en des matières de moulage thermoplastiques selon les revendications 1 à 9.
EP01986308A 2000-10-06 2001-09-24 Procede de preparation de latex caoutchouteux greffes ayant une teneur limitee en monomeres residuels Expired - Lifetime EP1326904B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10049466 2000-10-06
DE10049466A DE10049466A1 (de) 2000-10-06 2000-10-06 Verfahren zur Herstellung von Pfropfkautschuklatices mit reduziertem Restmonomerengehalt
PCT/EP2001/011013 WO2002028931A1 (fr) 2000-10-06 2001-09-24 Procede de preparation de latex caoutchouteux greffes ayant une teneur limitee en monomeres residuels

Publications (2)

Publication Number Publication Date
EP1326904A1 EP1326904A1 (fr) 2003-07-16
EP1326904B1 true EP1326904B1 (fr) 2010-03-10

Family

ID=7658858

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01986308A Expired - Lifetime EP1326904B1 (fr) 2000-10-06 2001-09-24 Procede de preparation de latex caoutchouteux greffes ayant une teneur limitee en monomeres residuels

Country Status (11)

Country Link
US (1) US6620883B2 (fr)
EP (1) EP1326904B1 (fr)
JP (1) JP2004510852A (fr)
KR (1) KR100821429B1 (fr)
CN (1) CN1269859C (fr)
AT (1) ATE460440T1 (fr)
AU (1) AU2002218193A1 (fr)
DE (2) DE10049466A1 (fr)
ES (1) ES2341225T3 (fr)
MX (1) MXPA03002935A (fr)
WO (1) WO2002028931A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10318109A1 (de) * 2003-04-22 2004-11-11 Bayer Ag Verfahren und Vorrichtung zur Herstellung elastomermodifizierten Thermoplasten
KR101126016B1 (ko) * 2005-10-04 2012-03-19 주식회사 엘지화학 잔류 단량체 함량이 낮은 그라프트 고무 라텍스의 제조방법
WO2008020012A2 (fr) 2006-08-18 2008-02-21 Basf Se Matières à mouler thermoplastiques à base d'acrylnitrile, de styrol et de butadiène
US7999040B2 (en) * 2007-09-25 2011-08-16 Nanochem Solutions, Inc. Method of making graft copolymers from sodium poly(aspartate) and the resulting graft copolymer
CN102027067B (zh) * 2008-02-08 2014-03-26 埃姆斯专利股份公司 耐水解性聚酰胺弹性体混合物、由该混合物生产的成型件及该混合物的用途
EP2566921B1 (fr) 2010-05-07 2014-04-16 Styrolution GmbH Masse de matière à mouler à dispersion de la lumière réduite
US8440764B2 (en) 2010-05-07 2013-05-14 Styrolution GmbH Molding composition with reduced light scattering
KR101401098B1 (ko) * 2010-09-29 2014-05-29 주식회사 엘지화학 Ａｂｓ계 그라프트 공중합체의 제조방법
WO2015047038A1 (fr) * 2013-09-30 2015-04-02 (주) 엘지화학 Procédé de préparation de copolymère greffé abs
CN105189588B (zh) * 2013-09-30 2017-09-12 Lg化学株式会社 一种制备abs接枝共聚物的方法
CN104693636B (zh) * 2013-12-06 2017-07-14 中国石油天然气股份有限公司 一种具有提高abs接枝共聚物转化率的聚合方法
US10525439B2 (en) 2015-04-10 2020-01-07 Ineos Styrolution Group Gmbh Process for the production of thermoplastic moulding compounds
EP3307425A1 (fr) 2015-06-12 2018-04-18 INEOS Styrolution Group GmbH Procédé de production de composés de moulage thermoplastiques
KR20210069031A (ko) 2018-07-24 2021-06-10 이네오스 스티롤루션 그룹 게엠베하 폴리아크릴레이트 그라프트 고무 코폴리머 및 충격 개질된 열가소성 성형 조성물
WO2020020834A1 (fr) 2018-07-24 2020-01-30 Ineos Styrolution Group Gmbh Copolymère de caoutchouc greffé de polyacrylate et composition de moulage thermoplastique
KR20220117262A (ko) 2019-12-17 2022-08-23 이네오스 스티롤루션 그룹 게엠베하 스티렌/아크릴로니트릴에 의한 폴리부타디엔 라텍스의 이중 개시제 그라프팅 공정
KR20240012450A (ko) 2021-05-25 2024-01-29 이네오스 스티롤루션 그룹 게엠베하 우수한 저온 충격 강도를 갖는 열가소성 물질을 위한 아크릴 고무

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7708002A (nl) * 1977-07-19 1979-01-23 Stamicarbon Werkwijze voor het bereiden van vinylpolymeren.
US4242469A (en) * 1978-09-18 1980-12-30 Cy/Ro Industries Controlling grafted elastomers in blends with resinous copolymers
NL8004698A (nl) * 1980-08-20 1982-03-16 Stamicarbon Werkwijze voor het bereiden van een copolymeer.
DE3638704A1 (de) * 1986-11-13 1988-05-26 Bayer Ag Abs-formmassen mit reduziertem restbutadiengehalt
NL8700292A (nl) * 1987-02-09 1988-09-01 Stamicarbon Werkwijze ter vervaardiging van een thermoplastische kunststof met hoge monomeer-conversie.
DE4130104A1 (de) * 1991-09-11 1993-03-18 Bayer Ag Verfahren zur herstellung von pfropfkautschuken unter reduzierter koagulatbildung
US6391965B1 (en) * 1996-05-31 2002-05-21 Mitsui Chemicals, Inc. Production process of ABS resin, ABS resin, and ABS-polycarbonate resin composition making use of the same
DE19741188A1 (de) 1997-09-18 1999-03-25 Basf Ag Verfahren zur Verminderung des Restmonomerengehalts in wässrigen Polymerdispersionen
DE19831734A1 (de) * 1998-07-15 2000-01-20 Bayer Ag Thermoplastische Formmassen auf Basis spezieller hocheffektiver Pfropfpolymerkomponenten
DE19839199A1 (de) 1998-08-28 2000-03-02 Basf Ag Verfahren zur Verminderung der Restmonomerenmenge in wässrigen Polymerdispersionen
DE19840586A1 (de) * 1998-09-05 2000-03-09 Basf Ag Verfahren zur Verminderung der Restmonomerenmenge in wässrigen Polymerdispersionen

Also Published As

Publication number Publication date
AU2002218193A1 (en) 2002-04-15
EP1326904A1 (fr) 2003-07-16
DE10049466A1 (de) 2002-04-11
KR20030051702A (ko) 2003-06-25
CN1468268A (zh) 2004-01-14
ES2341225T3 (es) 2010-06-17
US20020111435A1 (en) 2002-08-15
DE50115383D1 (de) 2010-04-22
US6620883B2 (en) 2003-09-16
MXPA03002935A (es) 2004-05-04
ATE460440T1 (de) 2010-03-15
WO2002028931A1 (fr) 2002-04-11
CN1269859C (zh) 2006-08-16
JP2004510852A (ja) 2004-04-08
KR100821429B1 (ko) 2008-04-10

Similar Documents

Publication Publication Date Title
EP0845497B1 (fr) Masses à moules thermoplastiques améliorées du type ABS
EP1268662B1 (fr) Compositions polymeres a constance de proprietes amelioree
EP1326904B1 (fr) Procede de preparation de latex caoutchouteux greffes ayant une teneur limitee en monomeres residuels
EP0845496A2 (fr) Masses à mouler à brillance élevée du type ABS
EP1263822B1 (fr) Procédé de préparation de compositions polymères ayant une meilleure constance des propriétés
EP1263879B1 (fr) Matieres a mouler abs ayant une moulabilite amelioree et une brillance elevee
EP1098918B1 (fr) Matieres moulables thermodurcissables a base de composants en caoutchouc greffe a haute efficacite
DE19520286A1 (de) ABS-Formmassen mit verbesserten Eigenschaften
EP1214375B1 (fr) Matieres de moulage thermoplastiques a base de constituants caoutchoutes greffes determines
WO2000029458A1 (fr) Matiere moulable abs aux associations de proprietes ameliorees
EP0731138A2 (fr) Masses à mouler thermoplastiques de type ABS
EP1098919B1 (fr) Matieres moulables thermodurcissables a base de composants polymere greffe a tres haute efficacite
DE102006056523A1 (de) Verfahren zur Herstellung von Pfropfkautschuken, Pfropfkautschuke und thermoplastische Formmassen auf Basis dieser Pfropfkautschuke
EP1414899B1 (fr) Compositions de polymeres a constance de proprietes amelioree
WO2000037559A1 (fr) Matieres moulables abs hautement resistantes aux chocs
EP1268664B1 (fr) Matieres moulables thermoplastiques a base de composants speciaux de caoutchouc greffe
EP1337569B1 (fr) Polymeres greffes elasto-thermoplastiques ameliores, destines a la production de matieres a mouler thermoplastiques modifiees par caoutchouc
DE102007035462A1 (de) Verfahren zur Herstellung von Pfropfkautschuken
DE102007045959A1 (de) Verfahren zur Herstellung von Kautschuklatices mit definiertem stabilem Gelgehalt für die ABS-Herstellung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030506

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17Q First examination report despatched

Effective date: 20040818

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LANXESS DEUTSCHLAND GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INEOS ABS (JERSEY) LIMITED

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 50115383

Country of ref document: DE

Date of ref document: 20100422

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2341225

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20100310

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100310

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100310

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100310

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100611

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100310

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100712

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100310

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100310

26N No opposition filed

Effective date: 20101213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100310

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100924

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100930

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100924

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100924

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100924

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100310

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20150928

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20160930

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20200929

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20201001

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 50115383

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20210925